Method of manufacturing semiconductor device

ABSTRACT

A method of manufacturing a semiconductor device includes a process for forming a photoresist pattern. In the disclosed process, residual photoresist polymers are removed using a photoresist polymer remover composition that includes: (a) 5% to 15% of sulfuric acid based on the total weight of said composition, (b) 1% to 5% of hydrogen peroxide or 0.0001% to 0.05% of ozone based on the total weight of said composition, (c) 0.1% to 5% of acetic acid based on the total weight of said composition, (d) 0.0001% to 0.5% of ammonium fluoride based on the total weight of said composition and (e) remaining amount of water.

TECHNICAL FIELD

[0001] Methods of manufacturing semiconductor devices using aphotoresist polymer remover composition are disclosed. The photoresistpolymer remover composition effectively removes photoresist residualsgenerated from etching or ashing sub-processes in photoresist patternforming processes during the manufacturing of semiconductor devices.

DESCRIPTION OF THE RELATED ART

[0002] In a conventional semiconductor device manufacturing process, aphotoresist pattern is formed on a conductive layer which has beenformed on a semiconductor substrate. The conductive layer whose portionis not covered by the pattern is etched using the photoresist pattern asa mask to form a conductive layer pattern. This lithography process isthen repeated to form the conductive patterns

[0003] The photoresist pattern is used as the mask and it should beremoved from the conductive layer with a photoresist remover in a stripprocess after the process for forming the conductive layer pattern iscompleted. However, it is difficult to remove photoresist material inthe subsequent strip process since the etching process for forming aconductive layer pattern is performed with a dry etching process whenmaking highly integrated devices and, as a result, the physical propertyof photoresist is deteriorated during the dry etching process.

[0004] Dry etching processes have replaced wet etching processes whichuse liquid acid compositions. In dry etching, gas-solid phase reactionare generated between a plasma etching gas and a conductive layer. Sincesharp patterns are obtained with dry etching processes and they are easyto control, dry etching processes are preferred to wet etchingprocesses.

[0005] However, during dry etching process, ions and radicals includedin the plasma etching gas cause a complicated chemical reaction on thesurface of a photoresist film which rapidly hardens the photoresistmaterial. In addition, a “puffing” phenomenon occurs, thereby generatinga residue of the photoresist material. As a result, it is difficult toremove the photoresist material.

[0006] Specifically, when the dry etching process is performed on metalconductive layers such as aluminum films, aluminum alloy films andtitanium nitride films, photoresist polymers on sidewalls of the metalconductive layer are chemically transformed and hardened. As a result,the photoresist polymers are not easily removed even by various removersin a strip process.

[0007] The currently available remover compositions including organicamine compounds and various organic solvents that are also used in thewet etching process. The available remover compositions typicallyinclude mono-ethanol-amine.

[0008] However, in current semiconductor device manufacturing processes,the above remover does not fully remove the photoresist materialprimarily because the photoresist material has been baked at hightemperatures because various substrates such as silicon wafers aretreated at a high temperature ranging from 110 to 140° C. The removercompositions containing water, hydroxyl amines or mixtures thereof havebeen developed for removing photoresist materials baked at hightemperatures.

[0009] Since the photoresist materials are exposed to plasma gas in dryetching or ashing processes which are used for manufacturing ultra highintegrated circuits, the remover compositions do not fully removephotoresist polymers which are chemically transformed and hardened. As aresult, development of photoresist removers to overcome theabove-described problem is needed.

[0010] A semiconductor substrate treated with the ashing process isconventionally heated at a high temperature of over 200° C. Here,residual solvent in the photoresist material should be vaporized andexhausted. However, a hardened layer which remains on the photoresistsurface after the ashing process prevents exhaustion of the residualsolvents. As a result, the surface of the photoresist film can be brokenor cracked by the residual solvent as internal pressure of thephotoresist film increases during the ashing process, which is called a“puffing” phenomenon.

[0011] Since the hardened layer shattered by the puffing phenomenonstill remains on the photoresist material, it is difficult to remove thephotoresist material with common removers. Such photoresist material istransformed into residues and particles, which may become polluters andcauses to lower yield rate in manufacture of ultra high integratedcircuits. When the ashing process is performed before the strip processto remove the photoresist material, the transformation of thephotoresist layer is deteriorated, which results in defects during thestrip process.

[0012] Of various ashing processes to effectively remove theabove-described transformed and hardened photoresist material, thetwo-step ashing process wherein the common ashing process is performedand then the second ashing process is re-performed is proposed(Fujimura, Digest of Papers 1989 2^(nd) MicroProcess Conference, Japan,pp. 196-197, 1989). However, since these processes are complicated andcomprise large-scale equipment, their production yield is degraded.

[0013] Only strip processes using compositions for removing photoresistpolymers have been used. Of the compositions, recently proposedphotoresist removers comprising hydroxyl amine, alkanol amine, corrosioninhibitor and water are extensively used because they are more effectiveto remove relatively transformed and hardened photoresist material.However, the above compositions do not fully remove photoresist polymerson metal lines or sidewalls of interlayer insulating films in productionline of semiconductors such as DRAMs of 256M or more where new metalfilms are used for metal lines or new insulating materials used forinterlayer insulating films. As a result, a photoresist remover tocomplement the above-described problem is also needed.

SUMMARY OF THE DISCLOSURE

[0014] Accordingly, improved photoresist polymer remover compositionsare disclosed, which effectively remove photoresist polymers formed onsidewalls and bottoms of lower films of the photoresist by dry etchingor ashing processes in processes for forming metal lines, via holepatterns and other patterns. When the lower films are metal films, thedisclosed photoresist polymer remover compositions minimize corrosion ofthe metal films.

BRIEF DESCRIPTION OF THE DRAWINGS

[0015]FIG. 1 is a SEM (Scanning Electron Microscope) photograph showinga photoresist pattern treated with a dry etching process or an ashingprocess.

[0016]FIG. 2 is a SEM photograph showing experimental results whenphotoresist polymers are removed at room temperature using a photoresistpolymer remover composition of Example 1 in accordance with thisdisclosure.

[0017]FIG. 3 is a SEM photograph showing experimental results whenphotoresist polymers are removed at room temperature using a photoresistpolymer remover composition of Comparative Example 2.

[0018]FIG. 4 is a SEM photograph showing experimental results of metalfilm corrosion at room temperature using the photoresist polymer removercomposition of Example 1 in accordance with this disclosure.

[0019]FIG. 5 is a SEM photograph showing experimental results of metalfilm corrosion at room temperature using a photoresist polymer removercomposition of Comparative Example 1.

DETAILED DESCRIPTION OF THE PRESENTLY PREFERRED EMBODIMENTS

[0020] A disclosed photoresist polymer remover composition comprising(a) sulfuric acid, (b) hydrogen peroxide or ozone, (c) acetic acid, (d)ammonium fluoride and (e) water.

[0021] One photoresist polymer remover composition comprises (a) 5% to15% of sulfiric acid based on the total weight of said composition, (b)1% to 5% of hydrogen peroxide or 0.0001% to 0.05% of ozone based on thetotal weight of said composition, (c) 0.1% to 5% of acetic acid based onthe total weight of said composition, (d) 0.0001% to 0.5% of ammoniumfluoride based on the total weight of said composition and (e) remainingamount of water.

[0022] The sulfuric acid is preferably present in an amount ranging from5 to 15 wt %, more preferably, from 7 to 10 wt %. Photoresist polymerdetergency may be degraded when the sulfuric acid is present in anamount of less than 5 wt % while metal films may be corroded when thesulfuric acid is present in an amount of more than 15 wt %.

[0023] The hydrogen peroxide is preferably present in an amount rangingfrom 1 to 5 wt %, more preferably, from 2 to 4 wt %. Photoresist polymerdetergency is degraded when the hydrogen peroxide is present in anamount of less than 1 wt % while economic efficiency is degraded whenthe hydrogen peroxide present in an amount of more than 5 wt %. Whenozone which is a strong oxidizer is used, photoresist residues may beeffectively removed by the ozone of small concentration. The ozone ispreferably present in an amount ranging from 0.0001 to 0.05 wt %, morepreferably, from 0.0002 to 0.001 wt %. The photoresist polymerdetergency of the disclosed solutions may be degraded when the ozone ispresent in an amount of less than 0.0001 wt % while economic efficiencymay be degraded when the ozone is present in an mount of more than 0.05wt %. The hydrogen peroxide and the ozone may be selectively used.

[0024] The acetic acid is preferably present in an amount ranging from0.1 to 5 wt %, more preferably, from 0.5 to 2 wt %. Photoresist polymerdetergency may be degraded when the acetic acid is present in an amountof less than 0.1 wt % while corrosion of metal films may be deepenedwhen the acetic acid is present in an amount of more than 5 wt %.

[0025] The ammonium fluoride is preferably present in an amount rangingfrom 0.0001 to 0.5 wt %, more preferably, from 0.01 to 0.05 wt %. Whenthe ammonium fluoride is present in an amount of less than 0.0001 wt %,it is difficult to completely remove transformed photoresist polymers onsidewalls and bottoms of lower films by dry etching and ashing processesin a pattern formation process. When the ammonium fluoride is present inan amount of more than 0.5 wt %, HSQ (Hydrogen Silsesquioxane) filmssuch as FOX (Flowable Oxide) films of stacked films in via hole patternsare corroded.

[0026] The disclosed photoresist polymer remover composition alsoincludes water, which is preferably pure water filtered through ionexchange resin, and more preferably ultra pure water having resistivityof 18 MΩ.

[0027] There is also provided a method of manufacturing a semiconductordevice where photoresist polymer residuals are removed using thedisclosed remover composition.

[0028] The above method comprises the steps of:

[0029] (a) preparing a semiconductor substrate on which an underlyinglayer is formed;

[0030] (b) forming a photoresist pattern on the underlying layer;

[0031] (c) selectively etching the underlying layer using thephotoresist pattern as an etching mask; and

[0032] (d) cleaning the resulting structure with the disclosed removercomposition to remove residual photoresist polymers, whereby forming theunderlying layer pattern.

[0033] In the above process, the underlying layer is a metal film or aninsulating film. Here, the metal film is preferably selected from thegroup consisting of aluminum film, aluminum alloy film, titanium film,titanium nitride film, tungsten film, and combinations thereof. In caseof stacked films, a stacked film comprising titanium nitridefilm/aluminum film/titanium film from the lower to the upper portion ispreferable. When the underlying layer is an insulating film, theinsulating film preferably is a HSQ film. In generally, a metal film isformed under the insulating film.

[0034] Any conventional photoresist polymers may be used for polymersincluded in the above photoresist.

[0035] The etching process in the step (c) is a dry etching process, andmay further comprise an ashing process to first remove a photoresistpattern after the dry etching process and before the step (d).

[0036] The photoresist pattern is formed by a photolithography process.Here, an exposure light source may be ArF (193 nm), KrF (248 nm), F₂(157 nm), EUV (13 nm), E-beam, X-ray or ion-beam. After and beforeexposure, a bake process is performed.

[0037] The underlying layer pattern may be an insulating film holepattern or a metal line/space pattern.

[0038] Instead of the photoresist pattern formation process using amask, a dry etching process such as an etch-back process or CMP(Chemical Mechanical Polishing) process is performed to clean theexposed photoresist film using the disclosed remover composition.

[0039] The cleaning process of the step (d) may be performed usingsingle-type or batch-type equipment. Although the cleaning condition maybe differentiated by states of the photoresist material to be removed,the photoresist material is soaked using chemicals at room temperatureor below 60° C. for about 10 to 60 seconds to completely removephotoresist polymers.

[0040] The disclosed photoresist polymer remover composition may easilyremove photoresist polymers formed on sidewalls and bottoms of the lowerfilms of photoresist by dry etching or ashing processes in recenthigh-integrated circuit semiconductor device manufacturing process formanufacturing semiconductor device within a short time. When the lowerfilm is an aluminium film, aluminum alloy film or tungsten film, thephotoresist polymer remover composition may effectively removephotoresist polymers formed on sidewalls of the lower metal film.

[0041] The disclosed remover composition effectively removes photoresistpolymers and minimizes corrosion of new lower metal films applied toyield line of ultra high integrated circuits such as DRAMs of over 256M.Also, the disclosed remover composition prevents an attack phenomenon onHSQ films such as FOX films of stacked films in the via hole patternformation process.

[0042] The disclosed photoresist polymer remover compositions will bedescribed in more details by referring to examples below, which are notintended to be limiting.

EXAMPLES 1-5 AND COMPARATIVE EXAMPLES 1-3 Preparation of PhotoresistPolymer Remover Composition

[0043] Each ingredient was mixed in ratios shown in the following table1 to obtain photoresist polymer remover compositions of Examples 1-5 andComparative Examples 1-3. TABLE 1 Composition Ingredient (wt %) (a) (b)(c) (d) Sulfuric Hydrogen Acetic Ammonium (e) acid peroxide ozone acidfluoride HF Water Example 1  5 5 — 2 0.05 — Residue 2 10 3 — 2 0.05 —Residue 3 10 5 — 0.5 0.05 — Residue 4 10 5 — 2 0.025 — Residue 5 10 —0.0005 2 0.05 — Residue Comparative 1 10 5 3 — 0.05 Residue Example 2 105 3 — — Residue 3 10 5 — 0.05 — Residue

[0044] Performance evaluation on the remover compositions of theExamples and Comparative Examples was performed by the following methodsof Experimental Examples.

EXPERIMENTAL EXAMPLE 1 Removal of Polymer (1) Preparation of Test sampleA

[0045] On an 8-inch silicon wafer where a titanium nitride film, analuminum film and a titanium film were sequentially deposited from thelower to the upper portion at 100 Å, 8000 Å and 400 Å, respectively, aconventional positive-type resist composition sold under the designation“DPR-i1000” by Dongjin Semichem Co. Ltd. was spin-coated to obtain aresist film of 1.01 μm. Thereafter, the resist film was pre-baked on ahot plate at 110° C. for 90 seconds. A mask having a predeterminedpattern was located on the resist film, and irradiated with ultravioletrays. Then, the exposed resist film was developed at 21° C. for 60seconds by TMAH developing solution of 2.38 wt % to form a photoresistpattern. A test sample where the photoresist pattern was formed washard-baked at 120° C. for 100 seconds on the hot plate. The titaniumnitride film, the aluminum film and the titanium film were etched usingthe photoresist pattern as a mask and Cl₂/BCl₃ mixed gas as etching gasin dry etching equipment (Applied Multireal Co., Model: DPS+) forEPD(End Point Detection)+45 seconds. Then, the ashing process wasperformed to remove most of the photoresist material using O₂ plasma,thereby obtaining Test sample A. FIG. 1 shows the cross-section of theTest sample A. Photoresist polymers still exist on sidewalls of the Testsample A.

(2) Removal of Photoresist Polymer

[0046] The Test sample A was soaked in each photoresist polymer removerof Examples 1-5 and Comparative Examples 1-3 at room temperature. TheTest sample A was washed with ultra pure water, and dehydrated withnitrogen gas. Then, whether photoresist polymer residuals were attachedon sidewalls of the pattern and on the surface of the line pattern wasexamined by the Scanning Electron Microscope (SEM, Hitachi Co. Ltd.,Model: S-5000) in order to evaluate polymer removal performance. Theexperimental results were shown in the following table 2, and FIGS. 2and 3. TABLE 2 Soaking Time 15 sec. 30 sec. 60 sec. Example 1 ◯ ◯ ◯ 2 ◯◯ ◯ 3 ◯ ◯ ◯ 4 ◯ ◯ ◯ 5 ◯ ◯ ◯ Comparative 1 ◯ ◯ ◯ Example 2 X X X 3 X X Δ

[0047] Referring to Table 2, the polymer removal performance of Examples1-5 and Comparative Example 1 was far superior to that of ComparativeExamples 2 and 3.

[0048]FIGS. 2 and 3 are SEM photographs showing experimental resultswhen photoresist polymers are removed using the photoresist polymerremover compositions of Example 1 and Comparative Example 2,respectively. The photoresist polymers were completely removed using theremover composition of Example 1 (see FIG. 2) while the photoresistpolymers were not completely removed using the remover composition ofComparative Example 2 (see FIG. 3).

EXPERIMENTAL EXAMPLE 2 Corrosion of Metal Film (1) Preparation of Testsample B

[0049] The procedure of Example 1 was repeated to obtain Test sample B.

(2) Experiment of Metal Film Corrosion

[0050] The Test sample B was soaked in each photoresist polymer removercomposition of Examples 1-5 and Comparative Examples 1-3 at roomtemperature. The Test sample B was washed with ultra pure water anddehydrated with nitrogen gas. Then, whether an undercut phenomenonoccurred in the lower metal film was examined by SEM to show corrosiondegree of the lower metal film. TABLE 3 Soaking Time 1 min. 3 min. 5min. Example 1 ◯ ◯ ◯ 2 ◯ ◯ ◯ 3 ◯ ◯ ◯ 4 ◯ ◯ ◯ 5 ◯ ◯ ◯ Comparative 1 X X XExample 2 ◯ ◯ ◯ 3 ◯ ◯ ◯

[0051] As shown in Table 3, the undercut phenomenon did not occur in thelower metal film after 5 minutes of the soaking time in Examples 1-5.However, in Comparative Example 1, the undercut phenomenon severelyoccurred in the lower metal film even the Test sample B was soaked for 1minute. Although the experimental results of metal film corrosion werepositive in Comparative Examples 2 and 3, most photoresist polymerresiduals were not removed on sidewalls and the surface of the linepattern as shown in Table 2. Accordingly, the remover composition ofComparative Examples 2 and 3 are not useful.

[0052]FIGS. 4 and 5 are SEM photographs showing experimental results ofmetal film corrosion at room temperature using a photoresist polymerremover composition of Example 1 and Comparative Example 1,respectively. The undercut phenomenon did not occur in the lower metalfilm when the remover composition of Example 1 was used (see FIG. 4).However, the undercut phenomenon severely occurred in the lower metalfilm when the remover composition of Comparative Example 1 was used (seeFIG. 5).

EXPERIMENTAL EXAMPLE 3 Application to Production Line

[0053] The evaluation results of a disclosed remover composition appliedto semiconductor device production line are shown in the followingtables 4 (hole pattern forming process) and 5 (line pattern formingprocess). TABLE 4 Device/Process Evaluation Item Evaluation Result 64MSDG/Process1 Polymer removability Completely removed Post-CleaningSidewall film (HSQ) attack None Titanium nitride film attack NoneForeign substance test on run No specific foreign substance, (KLAforeign substance test) No plug missing PT1(Probe Test)/PCM(Process Nosignificant difference Control Monitoring Test) compared to theconventional remover WFBM(Wafer Fail Bit Map) → No related fail M2Crelated fail PKG Test No significant difference compared to theconventional remover 256M DDR(BC)/Process1 Polymer removabilityCompletely removed Post-cleaning Sidewall film (HSQ) attack NoneTitanium nitride film attack None Foreign substance test on run Nospecific foreign substance (KLA foreign substance) PT1(Probe Test)/PCM(Process No significant difference Control Monitoring Test) compared tothe conventional remover

[0054] The detailed process represented in Table 4 is as follows.

(64MSD G/Process 1 Post-cleaning)

[0055] (1) A titanium film and a titanium nitride film were formed on asemiconductor substrate at 200 Å and 800 Å, respectively. (2) A tungsten(W) film was formed on the resulting structure at 4000 Å. (3) Thetungsten film was dry-etched by an etch-back process in dry-etchingequipment using SF₆ gas. (4) A titanium film, an aluminum-copper filmand a titanium nitride film were formed on the resulting structure at100 Å, 8000 Å and 400 Å, respectively. (5) A photoresist pattern wasformed on the resulting structure. (6) The metal line was dry-etchedusing the photoresist pattern as a mask in dry-etching equipment usingBCl₃/Cl₂ gas, and consecutively the photoresist film was removed usingO₂/CF₄/H₂O gas. (7) The wafer was treated with the disclosed removercomposition at 30° C. for 30 seconds while the wafer was rotated withsingle type wet cleaning equipment at 400 RPM (revolutions per minute).Then, the resulting wafer was washed with ultra pure water for 60seconds, and dehydrated using a spin dry at 2900 RPM for 30 seconds. Theexperimental results were shown in Table 4.

(256M DDR(BC)/Process1 Post-cleaning)

[0056] (1) A titanium film and a titanium nitride film were formed on asemiconductor substrate at 200 Å and 100 Å, respectively. (2) A tungsten(W) film was formed on the resulting structure at 4000 Å. (3) A titaniumfilm, an aluminum-copper film, a titanium film and a titanium nitridefilm were formed on the resulting structure at 100 Å, 4000 Å, 100 Å and750 Å, respectively. (4) A photoresist pattern was formed on theresulting structure. (5) The metal line was dry-etched using thephotoresist pattern as a mask in dry-etching equipment using BCl₃/Cl₂gas, and consecutively the photoresist film was removed using O₂/CF₄/H₂Ogas. (6) The wafer was treated with the disclosed remover composition at30° C. for 30 seconds while the wafer was rotated with single type wetcleaning equipment at 400 RPM. Then, the resulting wafer was washed withultra pure water for 60 seconds, and dehydrated using a spin dry at 2900RPM for 30 seconds. The experimental results were shown in Table 4.TABLE 5 Device/Process Evaluation Item Evaluation Result 256M DDR(BC)/Corrosion No corrosion Process2 Post-cleaning Polymer removabilityCompletely removed Sidewall film (metal such as Al) attack None andundercut Lower IMD(Inter Metal Dielectric) film None attack 128MDDR(BC)/ Corrosion No corrosion Process3 Post-cleaning Polymerremovability Completely removed Sidewall film (metal such as Al) attackNone and undercut Lower IMD (Inter Metal Dielectric) film None attackForeign substance test on run No specific foreign (KLA foreign substancetest) substance PT1(Probe Test)/PCM(Process Control No significantMonitoring Test) difference compared to the conventional remover

[0057] The detailed process represented in Table 5 is as follows.

(256M DDR(BC)/Process2 Post-cleaning)

[0058] (1) A titanium film and a titanium nitride film were formed on asemiconductor substrate at 200 Å and 800 Å, respectively. (2) A tungsten(W) film was formed on the resulting structure at 4000 Å. (3) Thetungsten film was dry-etched by an etch-back process in dry-etchingequipment using SF₆ gas. (4) A titanium film, an aluminum-copper filmand a titanium nitride film were formed on the resulting structure at100 Å, 8000 Å and 400 Å, respectively. (5) A photoresist pattern wasformed on the resulting structure. (6) The metal line was dry-etchedusing the photoresist pattern as a mask in dry-etching equipment usingBCl₃/Cl₂ gas, and consecutively the photoresist film was removed usingO₂/CF₄/H₂O gas. (7) The wafer was treated with the disclosed removercomposition at 30° C. for 30 seconds while the wafer was rotated withsingle type wet cleaning equipment at 400 RPM. Then, the resulting waferwas washed with ultra pure water for 60 seconds, and dehydrated using aspin dry at 2900 RPM for 30 seconds. The experimental results were shownin Table 5.

(128M DDR(BC)/Process3 Post-cleaning)

[0059] (1) A titanium film and a titanium nitride film were formed on asemiconductor substrate at 200 Å and 100 Å, respectively. (2) A tungsten(W) film was formed on the resulting structure at 4000 Å. (3) A titaniumfilm, an aluminum-copper film, a titanium film and a titanium nitridefilm were formed on the resulting structure at 100 Å, 4000 Å, 100 Å and750 Å, respectively. (4) A photoresist pattern was formed on theresulting structure. (6) The metal line was dry-etched using thephotoresist pattern as a mask in dry-etching equipment using BCl₃/Cl₂gas, and consecutively the photoresist film was removed using O₂/CF₄/H₂Ogas. (6) The wafer was treated with the disclosed remover composition at30° C. for 30 seconds while the wafer was rotated with single type wetcleaning equipment at 400 RPM. Then, the resulting wafer was washed withultra pure water for 60 seconds, and dehydrated using a spin dry at 2900RPM for 30 seconds. The experimental results were shown in Table 5.

[0060] Referring to Tables 4 and 5, when the disclosed removercomposition is applied to the actual production line, photoresistpolymers are shown to be completely removed using the disclosed removercomposition. Additionally, the problems such as corrosion, sidewallattack and undercut which are caused the residual polymers aftercleaning are not shown.

[0061] As discussed earlier, the disclosed photoresist polymer removercompositions may easily remove photoresist polymers formed on sidewallsand bottoms of the lower films of the photoresist by dry etching orashing processes in processes for forming metal lines, via hole patternsand other patterns within a short time. When the lower films are metalfilms, the photoresist polymer remover compositions may minimizecorrosion of the metal films.

What is claimed is:
 1. A method of manufacturing a semiconductor devicecomprising a process of forming a photoresist pattern using aphotoresist polymer remover composition, said composition comprising:(a) 5% to 15% of sulfuric acid based on the total weight of saidcomposition; (b) 1% to 5% of hydrogen peroxide or 0.0001% to 0.05% ofozone based on the total weight of said composition; (c) 0.1% to 5% ofacetic acid based on the total weight of said composition; (d) 0.0001%to 0.5% of ammonium fluoride based on the total weight of saidcomposition; and (e) remaining amount of water.
 2. The method accordingto claim 1, said composition comprising: (a) 7% to 10% of sulfuric acidbased on the total weight of said composition; (b) 2% to 4% of hydrogenperoxide or 0.0002% to 0.001% of ozone based on the total weight of saidcomposition; (c) 0.5% to 2% of acetic acid based on the total weight ofsaid composition; (d) 0.01% to 0.05% of ammonium fluoride based on thetotal weight of said composition; and (e) remaining amount of water. 3.The method according to claim 1, wherein the composition is furthercharacterized as a dry etching cleaner.
 4. The method according to claim1, wherein the process of forming a photoresist pattern comprises thesteps of: preparing a semiconductor substrate on which an underlyinglayer is formed; forming a photoresist pattern on the underlying layer;selectively etching the underlying layer using the photoresist patternas an etching mask; and cleaning the resulting structure using thephotoresist polymer remover composition to remove residual photoresistpolymers, whereby forming the underlying layer pattern.
 5. The methodaccording to claim 4, wherein the underlying layer is selected from thegroup consisting of aluminum film, aluminum alloy film, titanium film,titanium nitride film, tungsten film, and combinations thereof.
 6. Themethod according to claim 5, wherein the underlying layer is a stackedfilm where a titanium nitride film, an aluminum film and a titanium filmare sequentially deposited.
 7. The method according to claim 4, whereinthe underlying layer is an insulating film, and a metal film is formedunder the insulating film.
 8. The method according to claim 7, whereinthe underlying layer is a HSQ (Hydrogen Silsesquioxane) film.
 9. Themethod according to claim 4, further comprising the step of removing thephotoresist pattern by an ashing process after the etching and beforethe cleaning.
 10. The method according to claim 4, wherein thephotoresist pattern is formed by a photolithography process using ArF(193 nm), KrF (248 nm), F₂ (157 nm), EUV (13 nm), E-beam, X-ray orion-beam as an exposure light source.
 11. The method according to claim4, wherein said underlying layer pattern is an insulating film holepattern or metal line/space pattern.
 12. The method according to claim4, wherein the photoresist pattern is formed by an etch-back process orCMP (Chemical Mechanical Polishing) process.
 13. The method according toclaim 4, wherein the cleaning is performed using single-type or batchtype equipment.
 14. A semiconductor device manufactured by the method ofclaim
 4. 15. A method of cleaning a photoresist pattern using acomposition comprising: (a) 5% to 15% of sulfuric acid based on thetotal weight of said composition; (b) 1% to 5% of hydrogen peroxide or0.0001% to 0.05% of ozone based on the total weight of said composition;(c)
 0. 1% to 5% of acetic acid based on the total weight of saidcomposition; (d) 0.0001% to 0.5% of ammonium fluoride based on the totalweight of said composition; and (e) remaining amount of water.
 16. Aphotolithographic method comprising the steps of: forming a photoresistpattern on a semiconductor substrate; and cleaning the photoresistpattern using a photoresist polymer remover composition, saidcomposition comprising: (a) 5% to 15% of sulfuric acid based on thetotal weight of said composition; (b) 1% to 5% of hydrogen peroxide or0.0001% to 0.05% of ozone based on the total weight of said composition;(c)
 0. 1% to 5% of acetic acid based on the total weight of saidcomposition; (d) 0.0001% to 0.5% of ammonium fluoride based on the totalweight of said composition; and (e) remaining amount of water.